Peroxidation of free and esterified fatty acids by horseradish peroxidase

Linoleic and arachidonic acids and unsaturated esterified fatty acids of soybean lecithin liposomes were oxidized by horseradish peroxidase in the presence of hydrogen peroxide. The major products formed in the presence of oxygen were fatty acid hydroperoxides. In the absence of oxygen, other unidentified products were formed. Diene conjugation was about 5 times faster in oxygen than in nitrogen. Malondialdehyde was formed only in the presence of oxygen. Superoxide, singlet oxygen and hydroxyl radical may have been involved in the free fatty acid oxidation system but not in the liposome system. Replacement of hydrogen peroxide with the hydrogen peroxide (and superoxide) generators xanthine oxidase or galactose oxidase caused a more efficient oxidation in the presence of peroxidase than in its absence, suggesting that the in vivo toxicity of hydrogen peroxide and superoxide may be greatly increased in the presence of peroxidase.